Process of preparing phenyl-1-thioglycollic-2-carboxylic acid amides containing halogen



Patented Sept. 15, 1931 UNITED STATES nnruvmnn WAGNER, or BAD SoDEmmM- aa ;aagaassaarimo ?aaai siiam, AND RUDOLF BRUNE, or FRANKIE0R$-ON?HJI[E;MAIN-HOGH$T,A cnn v mnx, as-

SIGNORS TO GENERAL ANILINE WORKS, INC., 015 NEW YORK, N. Y., A CORPORATION OF DELAWARE PROCESS OF PREPARING PHENYL-l-IHIOGLY berating-tieredtam amass con- TAINING rrALo'GEn No firawing. Application filed December 12, 1928,

The present invention relates to a process of preparing phenyl-l-thioglycollic-2-carboxylic acid amides containing halogen.

1W6 have found that the phenyl-l-thmglycollic-fZ-carboxylic acid amides may be trans formed into halogen substitution products by treating them with a halogen, without the starting materials further being altered in any manner.

Furthermore we have found that the process may advantageously be carried out in such a manner that the halogenation is effected in the presence of a catalyst, for 1nstance of mercury, iodine or the like.

The following examples serve to illustrate our invention, but they are not intended to limit it thereto, the parts being by weight.

1. 26 parts of 3-methyl-5-chloro-phenyl-1 thioglycollic-2-carboxylic acid amide of the following formula:

OO.NH2

O S-OHQ-OOOH are dissolved in 250 parts of sulfuric acid of 66 B. into this solution 24: parts of bromine are run in drop by drop, while stirring at 20 C. to 25 G., the whole is then stirred and poured on ice. The precipitated product is filtered by suction, dissolved in a cold sodium carbonate solution and, after the solution has become clear, again precipitated by means of a mineral acid and then crystallized from mowed on ice, the Chlorination prcduict is glacial acetic acid. The thus purified 3- methyl-4Lbromo-5-chloro phenyl l-thioglycollic-Q-carboxylic acid amide melts at 195 C. to 196 C. The reaction product corre- 2. 26 parts of 3-methyl-5-chloro-phenyl- 1-thioglycollic-2-carboxylic acid amide are dissolved in 250 parts of sulfuric acid of 66 B. and into this solution about 9 parts of dry Serial No. and in dermany Mlay 5, 1925.-

chlorineare slowly introduced at about 0 C. After stirring for a prolonged time, the whole is pouredon ice; the chlorinationproduct is filtered by suction, dissolved in a cold sodium carbonate solution and after the solu'tion'has' become clear, again precipitated by means of a' mineral acid and thencrystallized from glacial acetic acid. The 3 rne'thyl-4.5 -dichloro-phenyl l thioglycollic Z-c'a'tboxylic acid amide is obtained melting at 204 C'. to

26'parts of' the 3-methyl-5-chloro-pha nyl-l' thioglycollic-2-carboXylic acid amide are 'diss'olved in 250 parts of sulfuric a cid'of 66 jB'., 02 part ofio'dine are added mamparts" of bromine are runin'dr'op by drop, while stirring at 20 Cito 25 the whole is subsequently stirred and" poured on ice. The precipitated product is'filtered' by suction, dissolved, in a cold sodium carbonate L solution and after the solution has become clear,again precipitated by means of a mineral acid and then crystallized from glacial acetic acid. The 3-methyl'-4;bromo-5-chloro-iphenyh1-thi'oglycollic-2-carboxylic acid amide thuspu'rified' melts at 195 Cfto v. 4, 26 parts tr 3- methy1-'5-chloro-phenyL1- thioglycollic-2rcarboxylic acid amide are (115- 'so'lvedjn 250 parts of sulfuric acid of 66 B.,

"tot/his solution 0.2 part of iodine are added and about 9 parts of dry chlorine are slowly win'tjroducedat about 0 C. After having stirredf'or a'prolonged; time, the whole is filtered by suction, dissolved in a coldsodium carbonate solution and after the solution has become clear, "again precipitated by means amide is obtained, melting at 204 C. to 2051C.

sulfuric acid also other diluents a phenyl-l-thioglycollic-Q-carboxylic acid ofamineral acid and then crystallized from glacial acetic acid, the 3-methyl-4 .5-dichlo- -:ro phenyl lthioglycollic Ql-carboxylic i acid a of iodine at a temperature between about 0 'furic acid of 66 tween about 0 C. and about 25 C.

, a free halogen of the amide to the action of a free halogen of the group consisting of chlorine and bromine in the presence of a diluent. o

2. The process which comprises subjecting 3-methyl-5-chloro-phenyl-l-thioglycolv lic-2-carboxylic acid amide to the action of a free halogen of the group consisting of chlorine and bromine in the presence of a diluent.

3. The process which comprises subjecting 3,-methyl-5-chloro-phenyl-l-thioglycollicr-2-carboxylic acid amide to the action of a free halogen of the group consisting of chlorine and bromine in the presence of sul- B. at a temperature be- 4. The process which comprises subjecting 3-methyl-5-chloro-phenyl-1-thioglycollic- 2-carboxylic acid amide tothe action of bromine which is run in drop by drop, while 1 stirring, in the presence of sulfuric acid of 66 B. at a temperature between about 20 MC. and about25 O.

' 5. The process which comprises subjecting 3-methyl-5rchloro-phenyl-l-thioglycollic- 2-carboXylic acid amide to the action of'a free halogen of the group consisting of chlorine and bromine in the presence of sulfuric acid of 66 B. andof a catalyst which favors aromatic ring halogenation at a temperature between about 0 C. and about 25 C.

6. The process which comprises subjecting 3-111ethyl-5-chlor0-phenyl-l-thioglycollic- 1 v2-carboXy1ic acid amide to the action of bromine which is run in drop by drop, while stirring, in thepresence of sulfuric acid of 66 Be. and of a catalyst which favors aromatic ring halogenation at-a temperature be- .tween about 20C. and about 25 C. Y 40 ing '4'. The process which'comprises subject- 3-methyl-5-chloro-phenyl-l-thioglycollic-2-carboxylic acid amide to the action of group consisting of the presence of sul- B. and of a small quantity chlorine and bromine in furlc acid of 66 C. and about 25 C.

8. The process which comprises subject- 7 ing 3-methyl-5-chloro-phenyl-l-thioglycollic-2-carboxylic acid amide to the action of bromine which is run in drop by drop, while ,stirring, in the presence of 66 B. and of a small quantity of iodine at between about 20 C. and

a temperature about 25 C. a

In testimony whereof, we alfix our signatures.

HERMANN WAGNER.

MAX HESSENLAND.

RUDOLF BRUNE.

sulfuric acid of y 

